Lubricating oils containing boron monothiophosphate



United States Patent 3,150,094 LUBRICATING OILS (IONTAINING BORON MONOTHIOPHOSPHATE Edwin L. De Young, Chicago, Ill., and Albert R. Sabol, Munster, Ind., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Filed Aug. 13, 1959, Ser. No. 833,406 1 Claim. (Cl. 252-46.7)

This invention relates to a new composition of matter, to a process for the preparation of the new composition of matter, and to a novel use of said new composition of matter.

Briefly described, the invention relates to the reaction 'of a dithiophosphate of the formula:

\IIELSH R20 with boric acid, i.e., B(OH) to form a boron monothiophosphate of the formula:

R and R are hydrocarbon radicals from the group consisting of aliphatic radicals of from about 1 to about 30 carbon atoms, cyclo aliphatic radicals of from about 4 to about 30 carbon atoms, and aromatic radicals of from about 6 to about 14 carbon atoms. The aromatic radicals can be mono nuclear or poly nuclear and can contain hydrocarbon substituents. R and R can be the same or can constitute different hydrocarbon radicals.

Examples of such aliphatic radicals are: methyl; ethyl; propyl; n-butyl; isobutyl; n-pentyl; isopentyl; neopentyl; n-hexyl; Z-methylpentyl; 3-methylpentyl; 2,2-dimethylbutyl; 2,3-dimethylbutyl; n-heptyl; Z-methylhexyl; 3-methylhexyl; 3-ethylpentyl; 2,2-dimethylpentyl; 2,3-dimethylpentyl; 2,4-dimethylpentyl; 3,3-dimethylpentyl; 2,2,3-trimethylbutyl; n-octyl; Z-methylheptyl; 3-methylheptyl; 2,2- dimethylhexyl; 2,3-dimethylhexyl; 2,5-dimethylhexyl; 3,4- dimethylhexyl; 2,2,3-trimethylpentyl; 2,2,4-trimethylpentyl; 2,3,3-trimethylpentyl; 2,3,4-trimethylpentyl; n-nonyl; n-decyl; n-undecyl; n-hexadecyl; n-octadecyl; n-eicosyl; n-triacontyi; ethenyl; propenyl; l-butenyl; Z-butenyl; cis and trans methylpropenyl; l-pentenyl; Z-pentenyl; cis and trans Z-methyl-Z-butenyl; l-hexenyl; 3-hexenyl (trans-); 3 methyl l-pentenyl; Z-methyl-Z-pentenyl; 3-methyl-2- pentenyl; cis and trans 2,3-dirnethyl-2-butenyl; 3,3-dimethyl-l-butenyl; 2,4,4-trimethyl-l-pentenyl; 2,3,4-trimethyl- 2-pentenyl; 2,4,4-trimethy1-2-pentenyl; cis and trans 3,4,4- trimethyl-Z-pentenyl; l-hexadecenyl; l-hexacosenyl; l-triacontenyl; allyl; 1,3-butadienyl; 1,3-pentadienyl; cis and trans isoprenyl; 1,5-hexadienyl; cis and trans 2,4-hexadienyl; cis and trans Z-methyl-l; 3-pentadienyl; 4-methyl- 1,3-pentadienyl; 1,3,5-hexatrienyl; ethynyl; propynyl; 1- butynyl; Z-butynyl; butenynyl; 1,5-hexadien-3-ynyl; 1,5,7- octatrien-S-ynyl; butadiynyl; 1,5-hexadiynyl; 2,4-hexadiynyl.

Examples of such cyclo aliphatic radicals are: cyclupropyl; cyclobutyl; methylcyclopropyl; cyclopentyl; cyclohexyl; methylcyclopentyl; methylcyclohexyl; ethylcyclopentyl; 1,1-dimethylcyclopenty1; cis and trans 1,2-dimethylcyclopentyl; cis and trans 1,3-dimethylcyclopentyl; cyclooctyl; ethylcyclohexyl; cis and trans 1,3-dimethylcyclohexyl; pmenthyl; cyclobutenyl; cyclopentenyl; cyclohexenyl; cyclooctenyl; 3-p-menthenyl; cyclopentadienyl; di-limonenyl; a-terpinenyl; ,B-phellandrenyl; cyclooctatetraenyl; p-caro- 3,150,094 Patented Sept. 22, 1964 ice tenyl; thujanyl; caranyl; pinanyl; camphanyl; cis and trans decahydronaphthyl; a-thujenyl; A -carenyl; t-pinenyl; bornylenyl; camphenyl; tricyclenyl; adamantanyl; dicyclopentadienyl.

Examples of such aromatic radicals are: phenyl; tolyl; o-xylyl; m-xylyl; p-xylyl; ethylphenyl; n-propylphenyl; rpropylphenyl; 1,2,3-trimethylpheny1; 1,2,4-trimethylphenyl; mesitylyl; p-cymyl; 1,3-diethylphenyl; 1,4-diethylphenyl; 1,2,3,4-tetramethylphenyl; 1,2,3,S-tetrarnethylphenyl; 1,2,4,5-tetramethylphenyl; hexamethylphenyl; n-dodecylphenyl; styryl; allylphenyl; l-phenyl=1,3-butadienyl; phenylethynyl; biphenyl; o-terphenyl; m-terphenyl; p-terphenyl; p-quaterphenyl; 1,3,5-triphenyl-phenyl; diphenylmethyl; 1,1-diphenylethyl; bibenzyl; stilbenyl; (trans-) triphenylmethyl; tetraphenylmethyl; tetraphenylethenyl; indenyl; naphthyl; 1,2,3,4-tetrahydronaphthyl; l-rnethylnaphthalene, Z-methylnaphthalene, fluorenyl; acenaphthanyl; acenaphthylenyl; anthracenyl; phenanthrenyl; fluoranthenyl; 15,16 dihydro 17H cyclopenta-(a)phenanthryl; naphthacyl; rubryl; benz(a)anthracyl; chrysenyl; triphenylyl; pyrenyl; cholanthryl; 3-methylcholanthryl; pentacyl; d1- benz(a,c)anthryl; dibenz(a,h)anthryl; picenyl; perylenyl; benzo(a)pyreny1; pyranthrenyl.

It is, therefore, an object of the present invention to provide a new composition of matter. It is a further object of this invention to provide a process for the manufacture of the new composition of matter. It is another object of this invention to provide an improved motor fuel. It is another object of this invention to provide an improved lubricating oil. It is a further object of this invention to provide a new pesticide. It is a further object of this invention to provide a motor fuel having inhibited surface ignition properties. It is a further object of this invention to provide a lubricating oil having inhibited silver, copper, and lead corrosion properties. It is a still further object of this invention to provide a lubricating oil having inhibited oxidation properties.

The following examples illustrate methods of preparing the new composition of matter but are not to be construed as limiting the invention:

EXAMPLE I Boron Di-n-Decyl Monothiophosphate The new composition was prepared by placing 785 g. of di-n-decyl dithiophosphate in a flask fitted with a stirrer, a thermometer, and a nitrogen purge tube. The next step included the addition of 39.6 g. of powdered boric acid to the flask which contained the dithiophosphate. The mixture of the di-n-decyl dithiophosphate and boric acid was heated to a temperature between 210 and 250 F. for one hour while utilizing nitrogen to purge the atmosphere within the flask. The reaction product resembled a pale yellow oil. Results of an analysis of the boron di-n-decyl monothiophosphate are as follows:

Molecular wt.:

Boron Di-Alkyl Monothiophosphate This composition was prepared by reacting P 8 with 70 mole percent isopropyl alcohol and 30 mole percent Percent B:

Calc. 1.42 Found .96 Percent P:

Calc. 12.0 Found 11.45 Percent S:

Calc. Found 15.96

The new boron monothiophosphates are, for the most ,part, oily liquids somewhat soluble in many organic solvents. They are particularly soluble in hydrocarbons. The boron monothiophosphates, when combined with a carrier, such as a spray or such as a dust composition, exert a definite toxicity against arachnids such as, for example, Tetranychus bimaculatus (two-spotted spider mite), Paratetranychus pilosus (European red mite), Bryobia praetiosa (clover mite) as well as certain small homopterous insects such as, for example, aphids. This pesticide gives excellent control of such organisms for extended periods of time.

The new toxicant may be used as a spray or as a dust compound. It may be employed in combination with an inert material carrier such as a finely divided solid, or a solvent liquid. The toxicant may be present in the inert carrier material in relatively high concentrations to provide a concentrate adapted for further dilution. It may also be present in the inert carrier material in dilute form to provide compositions suitable for application without further modification.

The following example illustrates the activity of the boron monothiophosphate as a pesticide:

EXAMPLE A A standard agricultural screening method was used to test the arachnids. The test included both the nympth and adult stage. A contact spray method was used within a Feet-Grady chamber. The chamber was operated at 5 p.s.i.g. One hundred organisms were placed on the bean plants. A concentration of 0.025% toxicant in acetone was sprayed on the bean plant. A count was made after 24 hours.

A standard agricultural screening method was used to test the aphididae family. The test included both the nympth and adult stage. A contact spray method was used within a Peet-Grady chamber. The chamber was operated at 5 p.s.i.g. One hundred organisms were placed on cotton plants. A concentration of 0.1% toxicant in acetone was sprayed on the cotton plant. A count was made after 24 hours.

Results obtained from the pesticide tests folow:

Pesticide Tests It has been proposed to add minor amounts of boron in the form of soluble or dispersable boron compounds to the liquid hydrocarbon fuels used in internal combustion engines. Among the compounds previously proposed for such purposes are the tri-alkyl borates and the tri-alkyl borines, such as tri-amyl borine and tri-isobutyl borate. This invention contemplates the addition of a boron compound which is soluble in a liquid hydrocarbon fuel and which compound contains phosphorus as well as boron.

A standard CFR L-head engine test utilizes an engine with a compression ratio of 7.0 to 1, a water temperature of 148 F. (:3 R), an oil temperature of 160 F. (i3 F.), and an air intake temperature of 110 F. (:5 F.). The test cycle is as follows:

Data obtained in a standard CRF L-head engine test are as follows:

Standard CFR L-Head Engine Test Base fuel,

Base fuel 2% boron Percent monothioreduction phosphate Surface ignition, counts/min. 350 70 These data demonstrate the utility of the boron monothiophosphate as a liquid hydrocarbon fuel additive.

A di-alkyl monothiophosphate was prepared by the reaction of P 5 with a mixture of 70 mole percent isopropyl alcohol and 30 mole percent oxodecyl alcohol and subsequent reaction with boric acid as set forth in Example II. This material was tested in a standard Timken testing machine. Such test is well known to those skilled in the art as being useful in obtaining valuable information with respect to the potential commercial value of extreme pressure lubricants. The Timken machine and test are fully described in the Journal of the Institute of Petro leum, 32, pages 209-210 and 220-222 (1946).

The data obtained for a base oil consisting of SAE-3O petroleum lubricating oil containing 3 weight percent of a barium-containing neutralized phosphorus-sulfide hydrocarbon reaction product detergent from the Timken testing machine are as follows:

These data demonstrate a substantial improvement in Timken load value resulting from the addition of a very small amount of boron monothiophosphate to a conventional petroleum lubricating oil.

The effectiveness of the boron compounds of the pres ent invention in inhibiting corrosion toward copper, silver and/or lead-containing metals and their oxidation inhibiting properties are demonstrated by data obtained by subjecting samples of the above metals to a Sand Stirring Corrosion Test. In this test a metal test specimen was slightly abraded with steel wool, Washed with naphtha, dried and weighed to the nearest mg. The cleaned test coupon was suspended in a steel beaker, cleaned with hot trisodium phosphate solution, rinsed with water, rinsed with acetone, and dried. An oil solution (250 g.) containing 1% di-n-decyl monothiophosphate was placed together with 0.625 g. lead oxide and 50 g. of a 30-35 mesh sand in the beaker. The beaker was then heated to a temperature of 300 F. (:2" F.) while the contents of the beaker were stirred by means of a stirrer which rotated at 750 r.p.m. The contents of the beaker were maintained at this temperature and under this condition for 48 hours after which the metal coupon was removed, rinsed with naphtha, dried, and weighed. Results of the test are as follows:

Sand Stirring Corrosion Test Wt. loss, mg. Material 48 hrs. 72 hrs.

Base oil 700 1. 000 Base oil 1% additive 55.1 71. 2

10% by weight of a boron phosphorus-containing compound having the formula:

wherein R and R are each the hydrocarbyl residue of an alcohol of a mixture of alcohols consisting of about 70 mole percent isopropyl alcohol and about mole percent decyl alcohol.

References Cited in the file of this patent UNITED STATES PATENTS 2,224,695 Prutton Dec. 10, 1940 2,346,156 Farrington et al Apr. 11, 1944 2,721,180 Lawrence et al. Oct. 18, 1955 2,743,235 McDermott Apr. 24, 1956 2,786,009 Pianfetti et a1 Mar. 19, 1957 2,809,163 Cyphers et al. Oct. 8, 1957 2,843,465 Yust et a1. July 15, 1958 2,885,430 Scherer et al. May 5, 1959 2,890,947 Annable et al June 16, 1959 2,920,993 Fairchild Jan. 12, 1960 2,922,812 Gilbert et al. Jan. 26, 1960 3,047,607 Thayer July 31, 1962 

